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Archive for 30.09.2016

Bioconjugate Chem, 2016, 27, 143-150

Статья пользователей РЦ МРМИ, попавшая на обложку журнала Bioconjugate Chemistry:

A.A. Belyaev, D.V. Krupenya, E.V. Grachova, V.V. Gurzhiy, A.S. Melnikov, P.Yu. Serdobintsev, E.S. Sinitsyna, E.G. Vlakh, T.B. Tennikova, S.P. Tunik

“Supramolecular AuI–CuI Complexes as New Luminescent Labels for Covalent Bioconjugation”

Bioconjugate Chem, 2016, 27, 143-150
DOI:10.1021/acs.bioconjchem.5b00563

источник: http://pubs.acs.org/doi/abs/10.1021/acs.bioconjchem.5b00563

Two new supramolecular organometallic complexes, namely, [Au6Cu2(C2C6H4CHO)6(PPh2C6H4PPh2)3](PF6)2 and [Au6Cu2(C2C6H4NCS)6(PPh2C6H4PPh2)3](PF6)2, with highly reactive aldehyde and isothiocyanate groups have been synthesized and characterized using X-ray crystallography, ESI mass spectrometry, and NMR spectroscopy. The compounds obtained demonstrated bright emission in solution with the excited-state lifetime in microsecond domain both under single- and two-photon excitation. The luminescent complexes were found to be suitable for bioconjugation in aqueous media. In particular, they are able to form the covalent conjugates with proteins of different molecular size (soybean trypsin inhibitor, human serum albumin, rabbit anti-HSA antibodies). The conjugates demonstrated a high level of the phosphorescent emission from the covalently bound label, excellent solubility, and high stability in physiological media. The highest quantum yield, storage stability, and luminance were detected for bioconjugates formed by covalent attachment of the aldehyde-bearing supramolecular AuI–CuI complex. The measured biological activity of one of the labeled model proteins clearly showed that introduced label did not prevent the biorecognition and specific protein–protein complex formation that was extremely important for the application of the conjugates in biomolecular detection and imaging.

Inorg. Chem., 2016, 55, 4720-4732

Статья пользователей РЦ МРМИ, попавшая на обложку журнала Inorganic Chemistry:

A.A. Penney, V.V. Sizov, E.V. Grachova, D.V. Krupenya, V.V. Gurzhiy, G.L. Starova, S.P. Tunik

“Aurophilicity in Action: Fine-Tuning the Gold(I)–Gold(I) Distance in the Excited State To Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)–NHC Complexes”

Inorg. Chem., 2016, 55, 4720-4732
DOI:10.1021/acs.inorgchem.5b02722

The formation of exciplexes between cationic dinuclear Au(I) bis(carbene) complexes and bromide ions was found to decrease the Au−Au distance in the triplet excited state, leading to pronounced changes in emission. The stimuli-responsive nature of the intracationic aurophilic interaction paves the way for fine-tuning the emission energy and opens new possibilities for practical applications.

Трофеи стажировки

vovk_sertificate_2016

Михаил Вовк успешно прошел курс “Advanced NMR methods” в рамках которого освещались: применение ямр термометров; настройка и применение shaped pulses для селективного возбуждения, адиабатической инверсии и развязки; 1D, 2D, 3D гомоядерные и гетероядерные корреляционные эксперименты с применением градиентных систем.

Изменения кадрового состава


Из РЦ МРМИ уволилась Эльвира Жиглей. Мы желаем нашему коллеге удачи на новом рабочем месте!

Конгресс Университета Арктики

кадры после трансляции

В рамках Конгресса Университета Арктики (12-16.09.2016, Санкт-Петербург; http://www.uarctic.spbu.ru/) П.М. Толстой выступил с докладом о работе Научного парка СПбГУ на примере РЦ «Магнитно-резонансные методы исследования». Был организован телемост с ресурсным центром, во время которого специалисты А.С. Мазур и М.А. Вовк отвечали на вопросы о текущей работе и выполняемых проектах.

Изменения кадрового состава


Мы рады приветствовать в наших рядах нового сотрудника, Романа Белых. Деятельность Романа направлена на расширение возможностей ЯМР/ЯКР спектрометра Tecmag Redstone.

Synthesis, 2016, 48, 2851-2862

M.S. Mishina, A.Yu. Ivanov, P.S. Lobanov, D.V. Dar’in

“A New Synthesis of 2-Aminoindoles and 6-Aminopyrrolo[3,2-d]pyrimidines from π-Deficient 1,2-Dihaloarenes and Geminal Enediamines”

Synthesis, 2016, 48, 2851-2862
DOI:10.1055/s-0035-1561645

источник: https://www.thieme-connect.de/products/ejournals/abstract/10.1055/s-0035-1561645

An efficient approach for the synthesis of fused 2-aminopyrroles via geminal enediamines and π-deficient 1,2-dihaloarenes is presented. The two-step methodology includes aromatic nucleophilic substitution of the activated halogen of dihaloarene with enediamine C-nucleophilic center followed by Cu-catalyzed intramolecular N-arylation. This approach allows access to a variety of 2-amino-6-nitroindoles and 6-aminopyrrolo[3,2-d]pyrimidines (including N-mono- and N,N-disubstituted) in moderate and good yields under mild conditions.

Cryst. Growth Des., 2016, 16, 2979-2987

E.S. Yandanova, D.M. Ivanov, M.L. Kuznetsov, A.G. Starikov, G.L. Starova, V.Yu. Kukushkin

“Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates”

Cryst. Growth Des., 2016, 16, 2979-2987
DOI:10.1021/acs.cgd.6b00346

источник: http://pubs.acs.org/doi/abs/10.1021/acs.cgd.6b00346

Reaction of K2[PtCl4] with excess AlkSCN in water gives the alkylthiocyanate complexes trans-[PtCl2(AlkSCN)2] (Alk = Et 1, nPr 2; 80–85%). These species were studied, in particular, by X-ray crystallography. In the solid state, both 1 and 2 exhibit the previously unreported S···Cl chalcogen bonding, which consolidates the complexes into networks and leads to layered structures. Theoretical density functional theory calculations and Bader’s atoms in molecules analysis demonstrated two types of intermolecular interactions in tetramer (1)4, viz. the S···Cl chalcogen and the H···Cl hydrogen bonds. Despite that each particular S···Cl or H···Cl bonding is weak with the estimated energy of 1–2 kcal/mol, altogether they play a crucial role in the stabilization of the S2Cl2 fragment in (1)4, the basis set of superposition error corrected interaction energy being −12.8 kcal/mol per monomer complex molecule. The chalcogen bonding and the rhomboidal structure of the S2Cl2 fragment can be interpreted in terms of electrostatic arguments as a result of the interaction between the belt of negative electrostatic potential around the Cl atoms and the sulfur σ-holes. The natural bond orbital analysis revealed that both LP(S) → LP*(Pt)/σ*(Pt–N)/σ*(Pt–Cl) and LP(Cl) → σ*(S–C) types of hyperconjugative charge transfers are important in the chalcogen bonding.

Август

В августе выполнено 1059 заявок на сервисные измерения.

Измерено:

  • 1006 спектров 1H
  • 192 спектра 13C
  • 79 спектров DEPT
  • 17 спектров COSY
  • 9 спектров NOESY
  • 2 спектра 31Р
  • 10 спектров 19F

Выполнено 129 заявок на исследовательскую работу.